Water-repellent textiles, and process for making same



Patented Nov. 10, 1942 UNITED STATES WATER-BEPELLENT TEXTILES, AND PROCESS FOR MAKING SAME Edgar Wolf, Kreleld,

' Germany, assignor to Heberlein Patent Corporation, New York, N. 1., a corporation of New York No Drawing 1938, Serial No.

plication June 17, 1939, Serial No. Germany March 15, 1937 11 Claims.

ally similar to the use of the water-repellent compounds and treatments disclosed in my copending application Ser. No. 177,054, filed No-' vember 29, 1937, Patent No. 2,294,435, reference to which is'hereby made. 7

I have found that in general the compounds derived from substituted ammonia-formaldehyde-condensation products can be converted with acid halides, and thereafter transformed by the addition of the tertiary bases into watersoluble compounds. 4

In accordance with this, I have also found that by the conversion of higher fatty chlorides with hexamethylenetetramine and subsequent treatment of the reaction product with tertiary bases such as pyridine .and others hereinafter mentioned, one may produce water-soluble, quaternary compounds. I have also found in accordance with my invention that such compounds comprise highly desirable products for the treatment of textile materials for water-repellence upon properly combining suchmaterials with such products under reaction conditions.

The objects of the invention accordingly include the provision of improved textiles rendered water-repellent by treatment with compounds of the above indicated character, and provision of improved processes for using the above-men- .tioned chemicals in producing such water-repellent textile materials, among other possible uses.

Further 'and'more specific objects, features and advantages of the invention will more fully appear from the following specification.

The invention consists in the novel products as well as the novel processes and steps of processes according to which such textile products are manufactured, specific embodiments thereof being described hereinafter by way of various examples according to which I now prefer to practice the invention.

In accordance with the present invention the acid halides above mentioned may have the general formula R.CO halide, in which R is an aliphatic or aliphatic-aromatic radical in which the aliphatic portion has at least ten carbon atoms. The conversion of such acid halides with hexa- Original application March 12,

195,800. Divided and this all- .methylenetetramine [(CHr) fected with a molar ratio of four parts of acid halide to one part of hexamethylenetetramine. The quantity of hexamethylenetetramine used, however, may also be increased for example to a ratio in the neighborhood of three mols of the acil halide to one mol of the hexamethylenetetramine. The resulting conversion products obtained in this manner may then be converted as by the use of pyridine, 2-methyl-pyridine, tri- .ethyl-amine, or equivalent tertiary bases, into quaternary ammonium compounds. Such compounds are remarkably effective in imparting water-repelling properties to textile material when properly applied thereto, in a manner generally similar to the application of the water-repellent chemicals to the textiles as disclosed by said copending application. The water-repelling effect is fast to washing or laundering with soap solutions and to dry cleaning with benzine for example. Furthermore, the fastness to washing of substantive dyestuffs where employed with the textile material so treated is substantially improved. And in connection with rayon fabrics produced from cellulose, it is possible by means of the process to effectively increase the fastness of such dyestuflfs both against deterioration by moisture and under dry conditions. Such compounds are also suitable for addition to baths serving for imparting creaseor wrinkle-resistant properties to textiles.

I may employ other substituted ammonia formaldehyde condensation products, instead of hexamethylenetetramine, for instance, a compound of the general formula R'.X.NH2 is first converted with formaldehyde or trioxymethylene. The converted product is treated with the acid halide. In the formula R.X.NH2, as herein used, R represents an alkyl radical (such for exam- 40 ple as C17H35), a cycloalkyl radical for example cyclohexylamine CsH1i.NH2, or an aralkyl radical (CmI-Iaaphenyl for example), and X indicates methylene or the C=O or SO: group. In place of the fatty acid chlorides, one may also use the corresponding chlorocarbonic acid ester (R.OCOC1) or carbamic acid chlorides (carbamido chlorides), such as CrsHsrNHCOCl, for example. As the tertiary bases to be used in such cases, one may for example use the volatile tertiary bases such as pyridine and its homologs, trimethylamine, triethylamine, etc. The resulting products may be used for the same purposes with substantially the same results above specifled in. connection with the previous embodiments 55 of the invention.

6N4] is preferably ef- The following are specific examples of the above described chemical products as made according to the invention and to the treatment of textiles therewith, carried out in various ways now preferred. It is to be understood that the invention is not limited to any of these particular examples or others as hereinafter given, except as indicated in the appended claims.

In the following examples the reaction between the fatty acid halide, carbonic ester halide, and carbamic acid halide with hexamethylenetetramine is conducted so that no decomposition of the hexamethylenetetramine into formaldehyde and ammonia occurs.

Examples for making the chemicals 1. 140 parts of hexamethylenetetramine are dissolved in 1400 parts of chloroform; 1208 parts of stearic acid chloride (C17H35COC1) are added and the whole is heated for one hour in a reflux condenser. The chloroform is thereupon drawn off by suction in vacuum and the conversion product is stirred with 320 parts of pyridine. There occurs the formation of the quaternary pyridinium compound with the simultaneous development of heat. The white wax-like mass obtained is now soluble in hot water; its melting point after recrystallization from petroleum ether is about 115 C. (with splitting off of formaldehyde).

2. 1208 parts of stearic acid chloride are diluted with about the same quantity of benzol or carbon tetrachloride and 140 parts of finely pulverized hexamethylenetetramine are added. After heating for two hours on a boiling water bath, the solvent is drawn off by suction in vacuum and the conversion product is stirred with 320 parts of pyridine. The wax-like resulting product is water-soluble. Its melting point is about 115 C.

3. 140 parts of hexamethylenetetramine are dissolved in 1400 parts of chloroform; thereupon, 1768 parts of montanic acid chloride C21H55.COC1 are added, and the whole is heated for one hour in the reflux condenser. The benzol is thereupon drawn oil by suction in vacuum and 320 parts of pyridine are stirred with the reaction product. The water-soluble wax-like compound obtained has a melting point of about 110 C.

4. 140 parts of finely pulverized hexamethylenetetramine are stirred with 1208 parts of stearic acid chloride and heated, while stirring constantly, for one hour, at about 110 C. Thereupon, 320 parts of pyridine are added, while stirring. The wax-like water-soluble product has a melting point of about 115 C.

5. 1350 grams of the conversion product obtained in accordance with Example 1 from stearic acid chloride and hexamethylenetetramine are mixed while stirring, with 372 grams of 2-methyl-pyridine. The quaternary pyridinium compound of 2-methyl-pyridine is produced with development of heat. The product is water-soluble.

6. 1350 grams of the conversion product obtained in accordance with Example 1, from stearic acid chloride and hexamethylenetetramine are stirred with 404 grams of triethylamine. The quaternary ammonium compound of triethylamine is produced with simultaneous development of heat. The product is water-soluble.

7. 140 parts of finely pulverized (powdered) hexamethylenetetramine are dissolved in 1400 parts of chloroform and 1340 parts of chlorocarbonic-acid-octadecyl-ester (octadecyl chlorcarbonate) C1aH37.0COCl are added; the whole is heated for one hour in the reflux condenser. the solvent is drawn off by suction in vacuum and to the residue, 320 parts of pyridine are added, while stirring. The product is water-soluble.

8. 850 grams of para-toluol sulfonamide CH:.C6H4.SO2NH2 are melted with 300 grams of trioxymethylene (CHaO): at a temperature of 110-120 C. until the condensation product is formed. Thereupon 1500 grams of stearyl chloride are added, the whole is well stirred and 400 grams of pyridine are added. The product is water-soluble.

9. 400 grams of stearic-acid-amide CnI-IaaCONHz are melted with grams of trioxymethylene (CI-I20): at a temperature of -120 C. until the condensation product is formed. Thereupon 350 grams of stearyl chloride are added and 150 grams of pyridine are added to the paste. The product is water-soluble,

10. 140 parts of hexamethylenetetramine are dissolved in 1400 parts of chloroform; 906 parts of stearic acid chloride (CmHasCOCl) are added and the whole is heated for one hour in a reflux condenser. The chloroform is thereupon drawn off by suction in vacuum and the conversion ,product is stirred with 240 parts of pyridine.

There occurs the formation of the quaternary pyridinium compound with the simultaneous development of heat. The white wax-like mass obtained is now soluble in hot water.

11. 140 vparts of hexamethylenetetramine are dissolved in 1400 parts of chloroform; 1692 grams of p-stearyl-oxy-benzoic-acid chloride (CnI-Ias.C0.0.phenyl.COCl) that I may employ the compounds without such addition of tertiary amine, or other water-solubilizing agent. If such material is omitted from the various compounds above, they are nevertheless useful for treatment of textiles in a similar manner to that herein described, but the treatment is preferably carried out by dissolving the compounds in benzine or similar solvent. An example of such treatment is given below.

The following comprise specific examples of methods now preferred for treating various textile materials according to the invention.

12. A cloak fabric which consists of spun rayon in warp and weft is impregnated in an aqueous solution which contains, per liter, 15 grams of the quaternary pyridinium compound prepared according to Example 1, from hexamethylenetetramine, stearic acid chloride and pyridine. The bath also contains 5 grams per liter of sodium acetate. The temperature of the bath is about 40 C. After the impregnation the material is dried and is then subjected for approximately one hour to a heat treatment in a drying chamber at about C.

13. Cotton calico is passed through an aqueous solution which contains 15 grams per liter of a quaternary pyridinium compound prepared according to Example 3 from hexamethylenetetramine, montanic acid chloride and pyridine. The bath also contains grams per liter of sodium acetate. The'said fabric is passed through said aqueous solution while the latter is at about 40 C. Thereafter the impregnated material is dried .and thereupon subjected to heat treatment in a drying chamber at about 120 C. for 2 hours.

14. Bleached wool gabardine is passed through an aqueous solution which contains 20 grams per liter of a quaternary pyridinium compound as described in Example 12. The impregnated material is dried and thereupon subjected to heat treatment in a drying chamber at about 90 C. for 4 hours.

15. A crepe de chine fabric which consists of real silk in warp and weft is impregnated in an aqueous solution which contains per liter grams of the quaternary pyridinium compound prepared according to Example 1, from hexamethylenetetramine, stearic acid chloride and pyridine. The bath also contains 5 grams per liter of sodium acetate. The temperature of the bath is about 40 C. Afterthe impregnation the material is dried and is then subjected for approximately two hours to a heat treatment in a drying chamber at about 110 C.

16. A clothing material of spun viscose rayon is impregnated in an aqueous solution of 5 grams per liter of sodium acetate, following the impregnation it is wrung out, dried, and passed through a 1% solution of the conversion product of hexamethylenetetramine and stearic acid chloride (Example 1 without pyridine) in carbon tetra chloride. The solvent is evaporated and the material is subjected for five minutes to a temperature of 110 C.

In consequence of the water-solubility of the quaternary ammonium compounds of my invention, the treatment of the textile material for the purpose of increasing the resistance to wetting and diminution of swelling capacity can advantageously be combined with a treatment for increasing the resistance to wrinkling, which is ordinarily carried out also in an aqueous bath; thus for the purpose of imparting water-repelling properties and wrinkle-resistance, a single aqueous bath may be employed containing not only the said quaternary ammonium compounds of my invention but also artificial resin or artificial resin initial condensation product or the formative components for the preparation of an artificial resin. Formaldehyde with ammonium chloride or other non-alkaline catalyst may be employed in place of the resin or resin components for producing wrinkle-resistance, and with this may be employed the quaternary ammonium compounds of my invention for producing waterrepellence. The processes thus employed in combination will produce a textile material having both water-repellence and wrinkle-resistance.

17. A plush fabric, consisting of cotton in warp and weft and artificial silk spun fiber in the pile. is passed through an aqueous bath which contains, per liter, 250 urea condensation product which is on the market under the name Kaurit," 6 grams of primary sodium phosphate, 6 grams of secondary sodium phosphate, 2 grams of tartaric acid, and 15 grams of the quaternary pyridinium salt prepared according to Example 3 from hexamethylenetetramine, montanic acid chloride and pyridine. After 7" amine combined grams'of a form'aldehyde- Formaldehyde 40% solution cc.. 40o Ammonium chloride grams 5 The quaternary pyridinium salt do 15 such as employed in Example 17.

After impregnation the material is squeezed out, rolled up and remains untreated for 20 minutes. The velvet is then stretched upon a stenter frame and dried at a temperature of about C. During the drying process the velvet'pile is brushed. After drying the velvet is further treated 60 minutes at a temperature of about C.

The new compounds described above can also be added to the spinning solutions of viscose and cuprammonium cellulose to produce a filament having water-repellent properties.

19. 20 parts of the quaternary ammonium compound obtained in accordance with Example 6 from stearic acid chloride, hexamethylenetetramine and trimethylamine are stirred to a paste with 40 parts of hot water, and are added to 1000 parts of a viscose solution having 5% of cellulose; the whole is homogeneously mixed and is spun in well-known fashion. The precipitating bath which I prefer to employ contains sulphuric acid (8-'-10%) with the addition of ammonium sulphate or any othersalts and glucose at a temperature of 40 C. The temperature and rate of spinning are substantially the same as those practiced commercially. The spun filament is dried and then heated to 90 C. for 60 minutes. The completed thread manifests water-repellent properties and is of extraordinary softness.

While the invention has been described in detail with respect to various preferred products and preferred methods of making the same, it will be obvious to those skilled in the art after understanding the invention, that further changes and modifications may be made therein without departing from the spirit or scope of the invention, and it is intended in the appended claims to cover all such changes and modificalOIlS.

What is claimed as new and desired to be secured by Letters Patent is:

1. Process for imparting permanent waterrepellence to cellulosic fabrics, which comprises: impregnating with a solution of a compound containing an aliphatic radical of at least ten carbon atoms, and comprising the product obtained by reacting a member of the group consisting of fatty acid halide, carbonic ester halide and carbamic acid halide, with hexamethylenetetramine,

in the presence of'heat and an inert solvent; drying the fabric soimpregnated; and heating to a sufficiently high temperature to impart said water-repellence.

2. Process for imparting permanent waterrepellence to cellulosic fabrics, which comprises:

- impregnating with an aqueous solution of a compound containing an aliphatic radical of at least ten carbon atoms, and comprising a tertiary with the product obtained by reacting a fatty acid halide with hexamethylenetetramine in the presence heat and an inert solvent; drying the fabric so impregnated; and heating to a sufllciently high temperature to impart said water-repellence.

3. Process for imparting permanent waterrepellence to cellulosic fabrics, which comprises: impregnating with an aqueous solution of a compound containing an aliphatic radical of at least ten carbon atoms, and comprising a tertiary amine combined with the product obtained by reacting a carbonic ester halide with hexamethylenetetramine in the presence of heat and an inert solvent; drying the fabric so impregnated; and heating toa sufficiently high temperature to impart said water-repellence.

4. Process for imparting permanent water repellence to cellulosic fabrics, which comprises: impregnating with an aqueous solution of a compound containing an aliphatic radical of at least ten carbon atoms, and comprising a tertiary amine combined with the product obtained by reacting a carbamic acid halide with hexamethylenetetramine in the presence of heat andan inert solvent; drying the fabric so impregnated; and heating to a sufllciently high temperature to impart said water-repellence.

5. A permanently water-repellent cellulosic fabric, having its fibers chemically treated by heating after impregnation with an aqueous solution of a compound containing an aliphatic radical of at leats ten carbon atoms, and comprising a tertiary amine combined with the product obtained by reacting a member of the group consisting of fatty acid halide, a carbonic ester halide and carbamic acid halide, with hexamethylenetetramine, under, conditions such that decomposition of the latter does not occur.

6. A permanently water-repellent cellulosicfabric having its fibers chemically treated by heating after impregnation with a compound containing an aliphatic radical of at least ten carbon atoms, and comprising a tertiary amine combined with the product obtained by reacting a fatty acid halide with hexamethylenetetramine, under conditions such that decomposition of the latter does not occur.

, 7. A permanently water-repellent cellulosic fabric having its fibers chemically treated by heating after impregnation with a compound containing an aliphatic radical of at least ten carbon atoms. and comprising a tertiary amine combined with the product obtained by reacting a carbonic ester halide with hexamethylenetetramine, under conditions such that decomposition of the latter does not occur.

8. A permanently water-repellent cellulosic fabric having its fibers chemically treated by heating. after impregnation with a compound containing an aliphatic radical of at least ten carbon atoms, and comprising a tertiary amine combined with the product obtained by reacting a carbamic acid 'halide with hexamethylenetetramine, under conditions such that decomposition of the latter does not occur.

9. Process for imparting permanent waterrepellence to cellulosic fabrics, which comprises: impregnating with an aqueous solution of a compound containing an aliphatic radical of at least ten carbon atoms and comprising a tertiary amine combined with the product obtained by reacting a member of the group consisting of fatty acid halide, carbonic ester halide and carbamic acid halide, with hexamethylenetetramine, under conditions such that decomposition of the latter does not occur; drying the fabric so impregnated; and heating at a sufliciently high temperature to impart said water-repellence.

10. Process for imparting permanent waterrepellence to cellulosic fabrics, which comprises: impregnating with an aqueous solution of a compound containing an aliphatic radical of at least ten carbon atoms, and comprising a tertiary amine combined with the product obtained by reacting 'a member of the group consisting of fatty acid halide, carbonic ester halide and carbamic acid halide, with hexamethylenetetramine .in the presence of heat and an inert solvent; drying\ the fabric so impregnated; and heating to a sufiiciently high temperature to impart said water-repellence.

11. A permanently water-repellent cellulosic fabric having its fibers chemically treated by heating after impregnation with a solution of a compound containing an aliphatic radical of at least ten carbon atoms, and comprising the product obtained by reacting a member of the group consisting of fatty acid halide, carbonic ester halide and carbamic acid halide, with hexamethylenetetramine, under conditions such that decomposition of the latter does not occur.

* EDGAR WOLF. 

